Monohaloalkenyl benzoates and trihaloalkyl benzoates

ABSTRACT

Monohaloalkenyl benzoates are halogenated to trihalo-substituted alkyl esters of benzoic acid. The halogenated compounds impart flame retardant properties to a variety of polymeric materials.

United States Patent 1 1 Gray et al.

[ Apr. 22, 1975 MONOHALOALKENYL BENZOATES AND TRIHALOALKYL BENZOATES [75] Inventors: Roy A. Gray; Donnie G. Brady, both of Bartlesville. Okla.

[73] Assignee: Phillips Petroleum Company,

Bartlesville. Okla.

[22] Filed: Apr. 19, 1972 [2l] Appl. No.: 245,387

[52] US. Cl.... 260/476 R; 260/4575 R; 260/4585; 260/469; 260/473 R UNITED STATES PATENTS 3.267.070 8/l966 Tousignant ct al. 260/476 R 3.7l6.59l 2/1973 Brady 260/476 R FOREIGNPATENTS OR APPLICATIONS 2.122.699 |2/|971 Germany 260/476 R OTHER PUBLICATIONS Chemical Abstracts, 22480c, Vol. 54.

Corey et al. Journal of the American Chemical Society. Vol. 89 pp. 2758 & 2759 (1967).

Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Patrick .I. Hagan 57 ABSTRACT Monohaloalkenyl benzoates are halogenated t0 trihalo-substituted alkyl esters of benzoic acid. The halogenated compounds impart flame retardant properties to a variety of polymeric materials.

9 Claims, No Drawings MONOHALOALKENYL BENZOATES AND TRIHALOALKYL BENZOATES FIELD OF THE INVENTION This invention relates to halogenated compounds. In another aspect, the invention relates to flame retarded polymeric compositions.

BACKGROUND OF THE INVENTION Flame retardancy has become a desired property for plastic articles used for commercial and household purposes, such as electrical insulation, carpeting, seat covers, and the like. Polymer compositions can be made difficulty flammable by the incorporation of various flameproofing agents. However, the ease of obtaining flame retardancy in a given polymer tends to vary from polymer to polymer. One type of polymer may be more effectively flame retarded than another, using the same amounts of additives; or, one type of polymer may require increased amounts of additives over the requirements of another type of polymer for each equivalent level of retardancy; or even one polymer species within a polymer class may require more or less flame retarded additive.

The search for novel compounds which can impart effective flame retardant properties to a variety of polymeric compositions continues.

OBJECTS OF THE INVENTION It is an object of our invention to provide novel compositions of matter. It is a further object of our invention to provide novel halogenatedorganic compounds. Another object of our invention is to provide novel polymeric compositions possessing improved flame resistance.

Other objects and aspects as well as the several advantages of our invention will be apparent to those skilled in the art to which the invention appertains from consideration of this specification including the appended claims.

BRIEF SUMMARY OF THE INVENTION We have discovered two groups of novel compounds. Novel unsaturated monohalo compounds which we have discovered can be termed monohaloalkenylbenzoate compounds. The benzoyl moiety thereof can be substituted, and the halogen of these monohaloalkenylbenzoates is chlorine, bromine, or iodine. These monohaloalkenylbenzoates can be halogenated to novel trihalo compounds, 2,3,4-trihaloalkylbenzoate compounds, in which the additional halogen can be chlorine, bromine, or iodine, the same or different from the first halogen. The 2,3,4-trihaloalkylbenzoate compounds impart effective flame retardancy to polymeric compositions. Polymeric compositions containing the novel halogenated compounds themselves are novel.

DETAILED DESCRIPTION OF .THE INVENTION Monohaloalkenylbenzoates The novel unsaturated monohaloalkenylbenzoate compounds can be descriptively termed 4-haloalkenyl benzoates. The compounds also can be represented by the general formula:

in which each R represents hydrogen or an alkyl, cycloalkyl, aryl, aralkyl, or alkaryl radical; and the halogen X is chlorine, bromine, or iodine. The R groups on the benzene ring each represent hydrogen or a radical such as alkyl, cycloalkyl, aralkyl, alkoxy, or halogen. When R is halogen, the halogen can be any one or more of fluorine, chlorine, bromine, or iodine. The integer indicator is 5. There appears to be no particular upper limitation in the size of a particular R or R group, as far as operabiiity is concerned. Presently preferred compounds fall into a sub-generic group such that the total number of carbon atoms per compound does not exceed about 20. Presently further preferred is a subgeneric group i of monohaloalkenyl benzoate compounds wherein each R is hydrogen and presently most preferred are the unsubstituted benzoates in which R is hydrogen.

Examples of the 4-haloalkenyl benzoates include: 4- chloro-2-butenyl benzoate, 4-bromo-2-butenyl benzoate, 4-iodo-2-butenyl benzoate, 4-chloro-2-butenyl ptoluate, 4-chloro-2-butenyl-3, S-dimethylbenzoate, 4-chloro-3-phenyl-2-butenyl benzoate, 4-bromo-2-ptolyl-2-butenyl 2,3,4,S-tetramethylbenzoate, 4-iodo-2- ethyl-3-phe'nyl-2-butenyl benzoate, 4-chloro-3- cyclohexyl-2-butenyl benzoate, 4-bromo-2-butenyl 2,4,6-tribromobenzoate, 4-chloro-2-butenyl 4-benzylbenzoate, 4-iodo-2-butenyl 3,5-dimethoxybenzoate 4- bromo-2,3-dimethyl-2-butenyl benzoate, 4-chloro-2-benzyl-2-butenyl 4-isopropylbenzoate, 4-iodo-2-ethyl-2-butenyl p-fluorobenzoate, 4-bromo-3-p-toIyl-2-butenyl 2,4-dichlorobenzoate, 4- chloro-2,3-diethyl-2-butenyl benzoate, 4-bromo-2- methyl-3-phenyl-2-butenyl 3,5-dibromobenzoate, 4-iodo-3-m-tolyl-2-butenyl benzoate, 4-chloro-2- butenyl 2,4,6-trimethylbenzoate, and the like, of which 4-chloro-2-butenyl benzoate is a presently preferred species.

The novel haloalkenyl esters represented by the general formula'(I) can be prepared by treating an alkali metal benzoate or substituted benzoate with a 1,4-

dihalo-2-alkene using a suitable catalyst such as a phosphine or quaternary phosphonium salt. The alkali metal of the alkali metal benzoate can be of any of lithium,

sodium, potassium, rubidium, or cesium. The benzoate.

radicals correspond as to substituents or lack thereof to the corresponding portion of the general formula (I) describing our novel monohalo unsaturated esters. The 1,4-dihalo-2-alkene reactant can be represented by the general formula:

11 a R n I I I I X-C-C=C-C-X 1,4-dihalo-2-butenes can be readily prepared by halogenation of l,3-butadiene or substituted 1,3-butadienes according to processes well known in the arts. Other examples of l,4-dihalo-2-alkene reactants include: 1,4- dichloro-2-phenyl-2-butene, 1,4-dibromo-2-methyl-2- butene, as well as others corresponding to the appropriate moieties for the described 4-haloalkenyl benzoates without repetitious listing, and the like.

Phosphine or phosphonium salt catalysts include those which can be represented by the general formulae R "'P or (R "'P),,,Y. The integer designator m can range from 1 to 3, and m is equal to the valence of Y. Y can be any anionic group with appropriate valence useful in quaternary phosphonium compounds as catalysts. R represents various hydrocarbon radicals such as alkyl, cycloalkyl, aryl, or any combination thereof, containing up to about carbon atoms per R' group, although this is governed by availability of materials rather than effectiveness or suitability. Examples of suitable phosphines include trimethyl phosphine, trioctyl phosphine, tricyclopentyl phosphine, triphenyl phosphine, tribenzyl phosphine, butylcyclohexylphenyl phosphine, and the like. Examples of quaternary phosphonium salts include ethyltriphenylphosphonium benzoate, tetraethylphosphonium acetate, tetraoctylphosphonium octanoate, tetra(4-tolyl)phosphonium 4- toluate, ethyltriphenylphosphonium chloride or fluoride or bromide, or any of the equivalent cyanide, cyanate, isocyanate, sulfate, phosphate, sulfonate, and the like quaternary phosphonium salts.

From about 0.1 to 50 moles or more of catalyst can be employed per 100 moles of alkali metal carboxylate employed in the reaction, although a range of about 0.5 mole to 10 moles presently is preferred.

As can be observed from consideration of the reaction, the equivalent ratio of the 1,4dihalo-2-alkene to the alkali metal benzoate is l:l,although a broad range can be employed of up to about 500:1 or even more, with a presently preferred range of about 2:1 to 10:1. It appears desirable to employ an excess of 1,4-dihalo- 2-alkene reactant in order to maximize yields of the desired haloalkenylbenzoate ester.

In general, any convenient contacting temperatures can be employed depending on the particular reactants and general reaction parameters. An exemplary temperatu're would be a range of about 50 C. to 200 C. Pressure preferably should be sufficient to maintain the reactants substantially in a liquid phase, such as from about 0.5 atmosphere to 10 atmospheres, depending to some extent on temperatures and diluents employed. Reaction'times sufficient to effect the degree of conversion desired should be employed, and range from a few minutes to upwards of 48 hours or more.

The treating of the alkali metal benzoate with the l,4-dihalo-2-alkene using the above-described catalysts preferably employs substantially anhydrous conditions, although minor traces of water often associated with the reactants do not interfere unduly.

The use of a diluent is a convenience, although the reaction can be carried out in excess 1,4-dihalo-2- alkene such that the 1,4-dihalo-2-alkene then acts both as reactant and as reaction medium or diluent, thus avoiding the use of an extraneous material. Examples of suitable diluents include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydropyran, cyclohexanone; any of the aromatic solvent hydrocarbons such as benzene, toluene, xylenes, and the like; aliphatic hydrocarbons such as pentane, hexane, and octane; tetrahydrofuran, N,N-dimethylformamide, cyclododecanone, N-methylpyrrolidone, and the like, alone, or in admixture with each other.

The resulting 4-haloalkenyl esters can be recovered by stripping, solvent extraction, distillation, and the like, as necessary or convenient.

Trihaloalkyl Benzoates The novel unsaturated monahalo esters of our invention are used to prepare novel 2,3,4-trihaloalkyl esters of benzoic acid which are a further part of our invention. The 2,3,4-trihaloalkyl esters of benzoic acid can be represented by the general formula:

0 HRRH l l I I )Q/ I III R; R xx E (III) wherein R, R, a and X, are as defined hereinbefore, with the halogens in the twoand three-position being the same.

The novel 2,3,4-trihaloalkyl benzoates conveniently are prepared by the addition of halogen to the corresponding 4-haloalkenyl esters. Such halogenation can be carried out at moderate temperatures, i.e., from about 20 to C., using a solvent such as chloroform, carbon tetrachloride, carbon disulfide, or the like, under halogenation conditions convenient for halogenation of unsaturated materials. A reaction interval of several minutes to several hours, such as from 1 hour to 12 hours, should be sufficient. If desired, a minor trace of hydrogen halide can be added as a catalyst, or a mixture of halogen and aluminum halide in an alcohol such as ethanol can be used. Generally an excess of halogen is avoided, so that a 1:1 molar ratio of halogen to unsaturated benzoate presently would be preferred. Examples of the novel trihalobenzoates include any of the hereinbefore described 4-haloalkenyl benzoates which have been halogenated so as to add halogen to v the double bond to become trihaloalkyl benzoates,

such as 4-chloro-2-butenyl benzoate to 2,3-dibromo-4- chlorobutyl benzoate, without needlessly repeating a list of exemplary species.

Flameproofed Polymer Compositions The novel trihalo compounds of our invention are useful as flame retardant additives for polymeric compositions. These additives can be employed, for example, in compositions of thermoplastic polymers.

Suitable polymers include any of the thermoplastic polymeric compositions such as the polydienes, i.e., the homopolymers and copolymers of conjugated dienes having from 4 to 10 carbon atoms per molecule, such as butadiene, piperylene, isoprene, chloroprene, 1,5- hexadiene, and the like, including copolymers with monovinyl-substituted aromatic compounds of up to 12 carbon atoms per molecule. Presently of importance because of wide textile usage are polymers of the aliphatic l-monoolefins known generally as polymonoolefins. These polymers include homopolymers and copolymers of aliphatic l-monoolefins having at least 2 carbon atoms per molecule, usually 2 to 8 carbon atoms for commercial availability, such as polyethylene, polypropylene, copolymers of ethylene and propylene, or copolymers of such monomers with minor amounts of monomers copolymerizable therewith such as ethylene, proplylene, l-butene, l-hexene, l-octene, monovinyl-substituted aromatic compounds of up to l2 carbon atoms such as styrene, alpha-vinyl naphthalene, p-isopropyl styrene, p-methyl styrene, and the like. Other polymeric substances employing flame retardants include a wide variety of other polymers such as the poly(vinyl halides) such as poly(vinyl chloride): cellulose: acrylic resins; and the like.

The trihaloalkyl esters of our invention should be employed in polymer compositions in such minor amounts as are effective in providing the desired degree of flame retardancy to the particular polymer or in the polymeric composition involved, which amount can vary over a broad range, depending on the polymer characteristics and the degree of protection desired or required. The presently preferred range of additive is about 3 to 30 parts per 100 parts of polymer, presently more preferred in an amount within the range of 5 to parts, excluding other additives, fillers, colorants, and the like.

Antimony oxide, presently preferred as the trioxide, can be employed with halogenated additives to enhance the effectiveness of organic flame retardants, such as from about 0.5 to parts of antimony trioxide per 100 parts of polymer. A typical weight ratio of halogenated additive to antimony oxide would be about 0.111 to 10:1, presently preferred about 2:1. Other useful oxides include bismuth oxide and arsenic trioxide which can be used, if desired, in place of or even with the antimony trioxide for this purpose,

Examples The examples and runs described herein are intended to illustrate our invention. Particular components described and conditions employed should be considered illustrative and not limitative of the reasonable scope and extent of our invention.

Example I To a dry stirred autoclave were added sodium benzoate 20 g, 0.14 mole, ethyltriphenylphosphonium bromide 1.2 g, 0.003 mole, and 1,4-dichloro-2-butene 37.5 g, 0.30 mole, in 50 ml of 2-butanone. The system was flushed with dry nitrogen. The stirred mixture was heated to 110 C., held at this temperature for 2.5 hours, then cooled to room temperature. The solid material was filtered off, washed with ml of 2- butanone, and air dried to give 8.8 g residue (8.2 g of NaCl theoretical).

The solvent in the filtrate was removed in vacuo to leave 43 g of a yellow liquid. Ether was added and the resulting tan solid removed by filtration and shown to be ethyltriphenylphosphonium bromide by infrared analysis.

The etheral filtrate was washed with 100 ml of distilled water and the organic layer was separated and dried over anhydrous magnesium sulfate. The ether was removed in vacuo to give a yellow liquid. Unreacted 1,4-dichloro-2-butene was removed by distillation b.p.ca. 60C/20mm. Fractionation of the remaining liquid gave 16 g of ester isolated as a clear colorless oil b.p. 100C/0.1mm. This liquid was shown by NMR analysis to be 4-chloro-2-butenyl benzoate.

Example II To a stirred reactor was added a solution of the 4- ature. The resulting straw colored solution was stirred overnight at room temperature. The solution was washed with distilled water, 5 per cent aqueous sodium bicarbonate, and again with distilled water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated in vacuo to leave 16.9 g of a colorless oil. Infrared and NMR spectra of this oil indicated it to be 2,3-dibromo-4-chlorobutyl benzoate.

Example Ill The following data demonstrate the flame retarding properties of the 2,3-dibromo-4-chlorobutyl benzoate in a polymer composition. Polypropylene was compounded with varying amounts of the trihalobenzoate and with antimony trioxide, the latter frequently employed to assist flame retarding effects of halogenated compounds, although by itself it exhibits no such properties.

TABLE I Limiting Benzoate, Sb O Oxygen Index phr phr ASTM D-2863 ASTM D-635 2 1 21.5 burned 3 1.5 23.4 burned 5 2.5 24.5 self-extinguishing to nonbuming These data demonstrate that the trihalobenzoates can be used for effective flame retarding in polymeric composition.

The polymeric compositions of our invention using the novel flame retardant can be compounded with other additives such as thermal stabilizers, fillers, pigments, dyes, plasticizers, and the like, any or all of which can be added to the formulation to improve stability and/or other properties of the final polymer composition for various purposes.

Reasonable variations and modifications of our invention are possible while still within the scope of our disclosure, and without departing from the intended scope and spirit thereof, as detailed in our specification and the claims appended.

We claim:

1. Unsaturated monohaloalkenyl benzoate compounds represented by the general formula:

wherein each R is individually selected from hydrogen, X or fluorine; R represents hydrogen; X is chlorine, bromine or iodine; a is 5; and wherein the total number of carbon atoms per monohaloalkenyl benzoate compound does not exceed 20.

2. Unsaturated monohaloalkenyl benzoate compounds according to claim 1 selected from the group consisting of 4-chloro-2-butenyl benzoate, 4-bromo-2- butenyl benzoate, 4-iodo-2-butenyl benzoate, and 4- bromo-2-butenyl-2,4,6-tribromobenzoate.

3. The monohaloalkenyl benzoate compounds according to claim 1 wherein R is hydrogen and X is chlorine and the species is 4-chloro-2-butenyl benzoate.

4. 2,3,4-Trihaloalkyl esters of benzoic acid represented by the general formula:

the group consisting of 2,3-dihalo-4-chlorobutyl benzoate, 2,3-dihalo-4- bromobutyl benzoate, 2,3-dihalo-4- iodobutyl benzoate, 2,3-dihalo-4-chlorobutyl p-toluate, 2,3-dihalo-4-chlorobutyl 3,5-dimethylbenzoate, 2,3- dihalo-4-chloro-3-phenylbutyl benzoate, 2,3-dihalo-4- bromo-2-p-tolylbutyl 2,3,4,5-tetramethylbenzoate, 2,3-

dihalo-4-iodo-2-ethyl-3-phenylbutyl benzoate, 2,3- dihalo-4-chloro-3-cyclohexylbutyl benzoate, 2,3- dihalo-4-bromobutyl 2,4,6-tribromobenzoate, 2,3- dihalo-4-bromo-2,B-dimethylbutyl benzoate, 2,3-

dihalo-4-chloro-2-benzylbutyl 4-isopropylbenzoate, 2,- 3-dihalo-4-iodo-2-ethylbutyl 4-fluorobenzoate, 2,3- dihalo-4-bromo-3-p-tolylbutyl 2,4-dichlorobenzoate, 2,3-dihalo-4-chloro-2,3-diethylbutyl benzoate, 2,3- dihalo-4-bromo-2-methyl-3-phenylbutyl 3,5- dibromobenzoate, 2,3-dihalo-4-iodo-3-m-tolylbutyl benzoate, and 2,3-dihalo-4-chlorobutyl 2,4,6-trimethylbenzoate.

6. The 2,3,4-trihaloalkyl esters of benzoic acid according to claim 4 wherein R is hydrogen.

7. The 2,3,4-trihaloalkyl esters of benzoic acid according to claim 6 wherein R is hydrogen.

8. The 2,3,4-trihaloalkyl esters of benzoic acid according to claim 7 wherein X is chlorine or bromine.

9. The 2,3,4-trihaloalkyl esters of benzoic acid according to claim 8 wherein each X in the 2 and 3 position is bromine and X in the 4 position is chlorine, and

the species is 2,3-dibromo-4-chlorobutyl benzoate. 

1. UNSATURATED MONOHALOALKENYL BENZOATE COMPOUNDS REPRESENTED BY THE GENERAL FORMULA:
 1. Unsaturated monohaloalkenyl benzoate compounds represented by the general formula:
 2. Unsaturated monohaloalkenyl bEnzoate compounds according to claim 1 selected from the group consisting of 4-chloro-2-butenyl benzoate, 4-bromo-2-butenyl benzoate, 4-iodo-2-butenyl benzoate, and 4-bromo-2-butenyl-2,4,6-tribromobenzoate.
 3. The monohaloalkenyl benzoate compounds according to claim 1 wherein R1 is hydrogen and X is chlorine and the species is 4-chloro-2-butenyl benzoate.
 4. 2,3,4-Trihaloalkyl esters of benzoic acid represented by the general formula:
 5. 2,3,4-trihaloalkyl esters of benzoic acid and substituted benzoic acids according to claim 4 selected from the group consisting of 2,3-dihalo-4-chlorobutyl benzoate, 2,3-dihalo-4-bromobutyl benzoate, 2,3-dihalo-4-iodobutyl benzoate, 2,3-dihalo-4-chlorobutyl p-toluate, 2,3-dihalo-4-chlorobutyl 3,5-dimethylbenzoate, 2,3-dihalo-4-chloro-3-phenylbutyl benzoate, 2, 3-dihalo-4-bromo-2-p-tolylbutyl 2,3,4,5-tetramethylbenzoate, 2,3-dihalo-4-iodo-2-ethyl-3-phenylbutyl benzoate, 2,3-dihalo-4-chloro-3-cyclohexylbutyl benzoate, 2,3-dihalo-4-bromobutyl 2,4,6-tribromobenzoate, 2,3-dihalo-4-bromo-2,3-dimethylbutyl benzoate, 2,3-dihalo-4-chloro-2-benzylbutyl 4-isopropylbenzoate, 2,3-dihalo-4-iodo-2-ethylbutyl 4-fluorobenzoate, 2,3-dihalo-4-bromo-3-p-tolylbutyl 2,4-dichlorobenzoate, 2,3-dihalo-4-chloro-2,3-diethylbutyl benzoate, 2,3-dihalo-4-bromo-2-methyl-3-phenylbutyl 3,5-dibromobenzoate, 2,3-dihalo-4-iodo-3-m-tolylbutyl benzoate, and 2,3-dihalo-4-chlorobutyl 2,4,6-trimethylbenzoate.
 6. The 2,3,4-trihaloalkyl esters of benzoic acid according to claim 4 wherein R'' is hydrogen.
 7. The 2,3,4-trihaloalkyl esters of benzoic acid according to claim 6 wherein R is hydrogen.
 8. The 2,3,4-trihaloalkyl esters of benzoic acid according to claim 7 wherein X is chlorine or bromine. 